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access(E)-4-Nitrobenzaldehyde oxime
aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, bDepartment of Forensic Medicine & Toxicology, National University of Sciences & Technology, Islamabad, Pakistan, and cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: profazmi@hotmail.com
In the title compound, C7H6N2O3, the planes containing the CNO and ONO atoms subtend dihedral angles of 5.47 (5) and 8.31 (5)°, respectively, with the benzene ring. In the intermolecular O—H⋯N hydrogen bonds link the molecules into centrosymmetric dimers with an R22(6) graph-set motif.
Related literature
For as therapeutic agents in organophosphorus poisoning, see: Jokanovic et al. (2009![[Jokanovic, M. & Prostran, M. (2009). Curr. Med. Chem. 16, 2177-2188.]](../../../../../../logos/arrows/e_arr.gif "Jokanovic, M. & Prostran, M. (2009). Curr. Med. Chem. 16, 2177-2188.")
); Marrs et al. (2006). For their use as protecting groups in organic synthesis, see: Greene et al. (1999); Shinada et al. (1995). For graph-set notation, see: Etter et al. (1990); Bernstein et al. (1995). For bond lengths in similar structures, see: Xing, Ding et al. (2007); Xing, Wang et al. (2007).
![[Scheme 1]](hg2672scheme1.gif)
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810013978/hg2672sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810013978/hg2672Isup2.hkl
To a warm solution of 4-nitrobenzaldehyde (0.907 g , 0.005 mol) in 25 ml e thanol, hydroxylamine hydrochloride (0.417 g, 0.006 mol) and sodium acetate trihydrate (2.04 g, 0.015 mol) were added and the mixture was heated under reflux until completion of the reaction. The concentrated reaction mixture was cooled down and water was added. The precipitated oxime was separated by filtration, washed with excess of water and dried. The crude product was recrystallized from ethanol to get the title compound (I).
All H atoms were placed in calculated position and treated as riding on their parent atoms with C—H = 0.93Å or O—H = 0.82Å with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O) for the hydroxyl H atom.
Thousands of deaths are caused by acute organophosphorus pesticide poisoning each year. are accepted therapeutic agents in organophosphorus poisoning (Jokanovic et al., 2009, Marrs et al., 2006). can act as useful protecting groups (Greene et al., 1999) and have served for the protection of carbonyl groups in the syntheses of erythromycin derivatives and perhydrohistrionicotoxin (Shinada et al., 1995). are also used for the purification and characterization of As part of our interest in the study of oxime derivatives, we report here the of the title compound (I). A depiction of the molecule is given in Fig. 1. In the of the title compound, molecules are connected via intermolecular O—H···N hydrogen bonds (see Table 1 and Fig. 2) to form two-dimensional dimers. The oxime group has an E configuration [C3—C7—N2—O3 = 179.1 (2)°] and the planes containing the CNO and ONO atoms subtend dihedral angles of 5.47 (5)° and 8.31 (5)° with the phenyl C(1–6) ring. which is less than that reported for similar structures (Xing & Ding et al., 2007; Xing & Wang et al., 2007). Each molecule is connected to a symmetry-related molecule through an inversion center by O—H···N hydrogen bonds, building an R22(6) graph-set motif in Fig. 2 (Etter et al., 1990; Bernstein et al., 1995; ).
For as therapeutic agents in organophosphorus
poisoning, see: Jokanovic et al. (2009); Marrs et al. (2006). For their use as protecting groups in organic synthesis, see: Greene et al. (1999); Shinada et al. (1995). For graph-set notation, see: Etter et al. (1990); Bernstein et al. (1995). For bond lengths in similar structures, see: Xing, Ding et al. (2007); Xing, Wang et al. (2007).
Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./hg2672fig1thm.gif) | Fig. 1. Molecular structure of (I) showing atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./hg2672fig2thm.gif) | Fig. 2. Hydrogen bonds shown as dashed lines, forming dimers through R22(6) graph set motif. |
| C7H6N2O3 | F(000) = 344 |
| Mr = 166.14 | Dx = 1.450 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1727 reflections |
| a = 3.7737 (2) Å | θ = 2.8–25.1° |
| b = 7.0363 (3) Å | µ = 0.12 mm−1 |
| c = 28.6651 (14) Å | T = 296 K |
| β = 91.237 (3)° | Block, colorless |
| V = 760.96 (6) Å3 | 0.49 × 0.41 × 0.16 mm |
| Z = 4 |
| Bruker APEXII CCD area-detector diffractometer | 1869 independent reflections |
| Radiation source: fine-focus sealed tube | 1340 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.031 |
| ω scans | θmax = 28.2°, θmin = 2.8° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −5→4 |
| Tmin = 0.945, Tmax = 0.982 | k = −9→9 |
| 7222 measured reflections | l = −38→37 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.175 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.060P)2 + 0.435P] where P = (Fo2 + 2Fc2)/3 |
| 1869 reflections | (Δ/σ)max < 0.001 |
| 110 parameters | Δρmax = 0.20 e Å−3 |
| 0 restraints | Δρmin = −0.20 e Å−3 |
| C7H6N2O3 | V = 760.96 (6) Å3 |
| Mr = 166.14 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 3.7737 (2) Å | µ = 0.12 mm−1 |
| b = 7.0363 (3) Å | T = 296 K |
| c = 28.6651 (14) Å | 0.49 × 0.41 × 0.16 mm |
| β = 91.237 (3)° |
| Bruker APEXII CCD area-detector diffractometer | 1869 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1340 reflections with I > 2σ(I) |
| Tmin = 0.945, Tmax = 0.982 | Rint = 0.031 |
| 7222 measured reflections |
| R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
| wR(F2) = 0.175 | H-atom parameters constrained |
| S = 1.09 | Δρmax = 0.20 e Å−3 |
| 1869 reflections | Δρmin = −0.20 e Å−3 |
| 110 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| O3 | 0.9103 (8) | 0.7939 (3) | −0.02398 (6) | 0.0848 (8) | |
| H3 | 0.9673 | 0.8950 | −0.0359 | 0.127* | |
| O2 | 0.2494 (7) | 0.1865 (3) | 0.14956 (8) | 0.0857 (8) | |
| N1 | 0.3651 (6) | 0.3009 (3) | 0.17705 (8) | 0.0575 (6) | |
| N2 | 0.8746 (6) | 0.8191 (3) | 0.02418 (7) | 0.0562 (6) | |
| C1 | 0.5229 (6) | 0.4774 (3) | 0.15885 (8) | 0.0425 (5) | |
| C2 | 0.5707 (6) | 0.4913 (3) | 0.11163 (8) | 0.0426 (5) | |
| H2 | 0.5092 | 0.3912 | 0.0919 | 0.051* | |
| C3 | 0.7126 (6) | 0.6576 (3) | 0.09400 (8) | 0.0415 (5) | |
| C7 | 0.7669 (7) | 0.6696 (3) | 0.04381 (9) | 0.0529 (6) | |
| H7 | 0.7205 | 0.5629 | 0.0255 | 0.063* | |
| C6 | 0.6116 (7) | 0.6200 (3) | 0.18954 (8) | 0.0509 (6) | |
| H6 | 0.5788 | 0.6059 | 0.2214 | 0.061* | |
| C5 | 0.7516 (7) | 0.7856 (3) | 0.17149 (9) | 0.0549 (6) | |
| H5 | 0.8135 | 0.8850 | 0.1914 | 0.066* | |
| C4 | 0.7997 (6) | 0.8040 (3) | 0.12444 (8) | 0.0474 (6) | |
| H4 | 0.8922 | 0.9165 | 0.1128 | 0.057* | |
| O1 | 0.3545 (8) | 0.2798 (4) | 0.21888 (8) | 0.1044 (9) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O3 | 0.143 (2) | 0.0654 (13) | 0.0469 (11) | −0.0300 (13) | 0.0171 (12) | 0.0024 (9) |
| O2 | 0.1130 (19) | 0.0472 (11) | 0.0966 (17) | −0.0354 (12) | −0.0037 (13) | 0.0100 (10) |
| N1 | 0.0583 (13) | 0.0447 (11) | 0.0694 (15) | −0.0043 (10) | 0.0033 (11) | 0.0160 (10) |
| N2 | 0.0732 (15) | 0.0490 (11) | 0.0467 (11) | −0.0115 (10) | 0.0070 (10) | 0.0029 (9) |
| C1 | 0.0405 (11) | 0.0353 (10) | 0.0518 (13) | −0.0014 (9) | 0.0023 (9) | 0.0071 (9) |
| C2 | 0.0467 (12) | 0.0318 (10) | 0.0491 (12) | −0.0054 (9) | −0.0020 (9) | −0.0028 (9) |
| C3 | 0.0432 (12) | 0.0335 (10) | 0.0478 (12) | −0.0031 (9) | −0.0004 (9) | 0.0015 (9) |
| C7 | 0.0677 (16) | 0.0416 (12) | 0.0496 (14) | −0.0128 (11) | 0.0028 (11) | −0.0025 (10) |
| C6 | 0.0586 (15) | 0.0501 (13) | 0.0442 (12) | 0.0019 (11) | 0.0022 (10) | 0.0012 (10) |
| C5 | 0.0706 (17) | 0.0410 (12) | 0.0528 (14) | −0.0082 (11) | −0.0034 (12) | −0.0077 (10) |
| C4 | 0.0543 (14) | 0.0332 (10) | 0.0544 (14) | −0.0095 (9) | −0.0020 (10) | 0.0008 (9) |
| O1 | 0.155 (3) | 0.0918 (17) | 0.0674 (15) | −0.0365 (17) | 0.0135 (14) | 0.0309 (12) |
| O3—N2 | 1.401 (3) | C2—H2 | 0.9300 |
| O3—H3 | 0.8200 | C3—C4 | 1.385 (3) |
| O2—N1 | 1.202 (3) | C3—C7 | 1.460 (3) |
| N1—O1 | 1.210 (3) | C7—H7 | 0.9300 |
| N1—C1 | 1.477 (3) | C6—C5 | 1.385 (3) |
| N2—C7 | 1.264 (3) | C6—H6 | 0.9300 |
| C1—C6 | 1.371 (3) | C5—C4 | 1.371 (3) |
| C1—C2 | 1.373 (3) | C5—H5 | 0.9300 |
| C2—C3 | 1.387 (3) | C4—H4 | 0.9300 |
| N2—O3—H3 | 109.5 | C2—C3—C7 | 118.11 (19) |
| O2—N1—O1 | 123.2 (2) | N2—C7—C3 | 122.7 (2) |
| O2—N1—C1 | 118.4 (2) | N2—C7—H7 | 118.7 |
| O1—N1—C1 | 118.4 (2) | C3—C7—H7 | 118.7 |
| C7—N2—O3 | 111.8 (2) | C1—C6—C5 | 117.8 (2) |
| C6—C1—C2 | 123.0 (2) | C1—C6—H6 | 121.1 |
| C6—C1—N1 | 118.9 (2) | C5—C6—H6 | 121.1 |
| C2—C1—N1 | 118.1 (2) | C4—C5—C6 | 120.4 (2) |
| C1—C2—C3 | 118.63 (19) | C4—C5—H5 | 119.8 |
| C1—C2—H2 | 120.7 | C6—C5—H5 | 119.8 |
| C3—C2—H2 | 120.7 | C5—C4—C3 | 121.0 (2) |
| C4—C3—C2 | 119.1 (2) | C5—C4—H4 | 119.5 |
| C4—C3—C7 | 122.78 (19) | C3—C4—H4 | 119.5 |
| O2—N1—C1—C6 | 171.2 (2) | C4—C3—C7—N2 | −5.0 (4) |
| O1—N1—C1—C6 | −7.8 (4) | C2—C3—C7—N2 | 175.6 (3) |
| O2—N1—C1—C2 | −8.2 (3) | C2—C1—C6—C5 | 0.8 (4) |
| O1—N1—C1—C2 | 172.8 (3) | N1—C1—C6—C5 | −178.6 (2) |
| C6—C1—C2—C3 | −0.5 (3) | C1—C6—C5—C4 | −0.2 (4) |
| N1—C1—C2—C3 | 178.8 (2) | C6—C5—C4—C3 | −0.5 (4) |
| C1—C2—C3—C4 | −0.3 (3) | C2—C3—C4—C5 | 0.8 (4) |
| C1—C2—C3—C7 | 179.1 (2) | C7—C3—C4—C5 | −178.6 (2) |
| O3—N2—C7—C3 | 179.1 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···N2i | 0.82 | 2.12 | 2.841 (3) | 146 |
| Symmetry code: (i) −x+2, −y+2, −z. |
Experimental details
| Crystal data | |
| Chemical formula | C7H6N2O3 |
| Mr | 166.14 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 296 |
| a, b, c (Å) | 3.7737 (2), 7.0363 (3), 28.6651 (14) |
| β (°) | 91.237 (3) |
| V (Å3) | 760.96 (6) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.12 |
| Crystal size (mm) | 0.49 × 0.41 × 0.16 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD area-detector |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
| Tmin, Tmax | 0.945, 0.982 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7222, 1869, 1340 |
| Rint | 0.031 |
| (sin θ/λ)max (Å−1) | 0.666 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.175, 1.09 |
| No. of reflections | 1869 |
| No. of parameters | 110 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.20, −0.20 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···N2i | 0.82 | 2.12 | 2.841 (3) | 146.2 |
| Symmetry code: (i) −x+2, −y+2, −z. |
Acknowledgements
AA is grateful to the HEC-Pakistan for financial support for his PhD program under scholarship No. [IIC–0317109].
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Thousands of deaths are caused by acute organophosphorus pesticide poisoning each year. Oximes are accepted therapeutic agents in organophosphorus poisoning (Jokanovic et al., 2009, Marrs et al., 2006). Oximes can act as useful protecting groups (Greene et al., 1999) and have served for the protection of carbonyl groups in the syntheses of erythromycin derivatives and perhydrohistrionicotoxin (Shinada et al., 1995). Oximes are also used for the purification and characterization of carbonyl compounds. As part of our interest in the study of oxime derivatives, we report here the crystal structure of the title compound (I). A depiction of the molecule is given in Fig. 1. In the crystal structure of the title compound, molecules are connected via intermolecular O—H···N hydrogen bonds (see Table 1 and Fig. 2) to form two-dimensional dimers. The oxime group has an E configuration [C3—C7—N2—O3 = 179.1 (2)°] and the planes containing the CNO and ONO atoms subtend dihedral angles of 5.47 (5)° and 8.31 (5)° with the phenyl C(1–6) ring. which is less than that reported for similar structures (Xing & Ding et al., 2007; Xing & Wang et al., 2007). Each molecule is connected to a symmetry-related molecule through an inversion center by O—H···N hydrogen bonds, building an R22(6) graph-set motif in Fig. 2 (Etter et al., 1990; Bernstein et al., 1995; ).